JPS61188533A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the excellent photosensitive composition by incorporating an alpha, beta-unsatd.ethylenic polymer, an alpha, beta-unsatd. ethylene compd. Which is capable of photocross-linking and is liquid at a room temp., a thioxanthone (derivative), a specific P-dialkylamino benzoic acid (ester) and a lophine dimer to the titled composition. CONSTITUTION:The titled composition comprises the resin contg. the alpha, beta-unsatd. ethylenic monomer as a constituting unit, the alpha, beta-unsatd. ethylene compd. Which is capable of photocross-linking and is liquid at the room temp., one or more of thioxanthone or its alkyl derivative or its halogen derivative, and one or more of the lophine kimer shown by formula I wherein R1 and R2 are 1-3 C alkyl, R3 is a hydrogen atom or <=18 C alkyl group, and formula II wherein a phenyl group may be substd. with Cl, F, OCH3. The titled composition is suitable to produce a printed wiring board and can form the photosensitive layer capable of forming the pattern having an excellent adhesion against a substrate and a resolution.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to photosensitive compositions.

(Prior art) □ Conventionally, a film of a photosensitive composition is formed by coating the photosensitive composition on a transparent support film, etc.
Bringing the film into contact with the surface of the substrate on which an image is to be drawn,
The film is made dense by heat-sealing, etc., and the transparent support film is left on the top layer. A solvent method in which the unexposed area is eluted using a melting chamber after exposure;
Alternatively, an image corresponding to the original image is developed by a peeling development method in which an unexposed portion is attached to and removed from the supporting film described above when the supporting film is peeled off, and this is used to produce, for example, a printed wiring board by a 7-resist method. It has been applied to the production of relief plates or used in the production of relief plates. 1) It is not possible to obtain a conventional photosensitive composition that satisfies the above-mentioned properties and properties at the same time. In addition, the adhesion to the substrate on which the image is to be formed is still insufficient, and as a result, satisfactory resolution cannot be obtained.
When mounting an IC chip on a printed wiring board, 5
However, it is difficult to meet such requirements in a manufacturing process where a resolution of 0μ or less is required.Furthermore, when used for forming copper through-hole circuits, the tent strength is weak.
The film thickness needs to be 50/1 or more; if it is thinner than this, the hole portion will be torn during development and the product will be defective.

More specifically, for example, as described in Japanese Patent Publication No. 48-3840'3, 2-4-
The combination of 5-triarylmethimidazolyl dimer and P-aminophenyl ketone is I! However, the sensitization speed is insufficient.

Furthermore, as described in Japanese Patent Publication No. 52-34490, a combination of thioxanthone or its halogenated derivative and P-diphenylaminobenzoic acid or its ester has been proposed, but the adhesion to the substrate is insufficient. Therefore, the resolution was not sufficient, and the tenting property was weak when used as a copper-through resist.

(Problems to be Solved by the Invention) In view of the above-mentioned current situation, the present invention has a high sensitization speed,
The purpose of this invention is to provide a photosensitive resin composition which has excellent storage stability, and is also excellent in resolution, etching resistance, tenting resistance, and plating resistance.

('Means for Solving the Problems) The gist of the present invention is to provide (a) a resin containing an α,β-unsaturated ethylenic monomer as a constituent unit, (b) a photocrosslinkable α of a liquid at room temperature.
, a β-unsaturated ethylenic compound, at least one of (cl thioxanthone or an alkyl or halogenated derivative thereof)
(d) at least one type of P-dialkylaminobenzoic acid or its esterified product represented by formula (I) (provided that the island and R1 are carbon & 1 to 3 alkyl groups, R
, dihydrogen or an alkyl group having 18 or less carbon atoms), , (e) at least 1.5-tria, 5-tria, ru imidazolyl dimer consisting of a b, fin dimer. The present invention relates to a photosensitive resin composition characterized in that it contains seeds.

The resin component (a) used in the present invention includes α, β
- A polymer substance having an unsaturated ethylenic monomer as a constituent unit is used, and examples of the α, β-, unsaturated ethylenic monomer include styrene%O-methylstyrene, m
-Methylstyrene, P-methylstyrene, α-dimethylstyrene, P-ethylstyrene, 2,4-dimethylstyrene, P-n-butylstyrene, P-tert-butylstyrene, Pn-hexylstyrene, P-n - Styrenes such as octylstyrene, P-methoxystyrene, P-phenylstyrene, 3,4-dichlorostyrene,
Vinyl naphthalene class 7; Ethylene, propylene, butylene, C1 to Cw and higher α-olephates; Vinyl halides such as vinyl chloride, vinyl bromide, vinyl fluoride, etc.: vinyl acetate, vinyl propionate, Vinyl esters such as vinyl butyrate*, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, butyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, acrylic acid 2 - Chlorethyl, phenyl acrylate, α-chloromethyl methacrylate, ethyl methacrylate, propyl methacrylate, a n -butyl methacrylate, isobutyl methacrylate, 12n-octyl methacrylate, lauryl methacrylate, methacrylic acid α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl, phenyl methacrylate, dimethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacriminitrile, acrylamide: vinyl methyl ether , vinyl ethers such as vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone; N-vinylvirol, N
-N- such as hinylcarhasol, N-vinylindole, etc.
Examples include vinyl compounds.

The photo-crosslinkable α,β-unsaturated ethylenic compound 1b) used in Zero-Ipplication #4 is a room-temperature liquid monomer that initiates polymerization and cures with light in the presence of photopolymerization initiation. Polymers such as pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, polymethylene diacrylate, polymethylene dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, etc. Examples include acrylate monomers and polymethacrylate monomers.

Examples of thioxanthone or its alkyl or non-rogenated derivative (c) used in the present invention include thioxanthone, alkylated derivatives of thioxanthone such as 2-ethylthioxanthone and 2,4-diethylthioxanthone, 2-chlorothioxanthone, 710-genated derivatives of thioxanthone such as 2,4-dichlorothioxanthone can be suitably used.

Examples of P-dialkylaminobenzoic acid or its esterified product (d) represented by formula (I) used in the present invention include P-dimethylbenzoic acid, P-diethylaminobenzoic acid, P-diisopropylamino Benzoic acid and esters thereof with the following alcohols can be used.

That is, examples of child alcohols that produce effects when subjected to esterification include methyl alcohol, ethyl alcohol, furoyl alcohol, isopropyl alcohol, methyl alcohol, and inbutyl alcohol.
'Cyl alcohol, tert-methyl alcohol, n-
alcohol, inoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol,
Caprylic alcohol, nonyl alcohol, tethyl alcohol;
Alcohols having a carbon content of 1 to 18 can be used, such as alcohol, undecyl alcohol, 9') alcohol, tridecyl alcohol, cetyl alcohol, and stearyl alcohol. These esterification reactions can be carried out using a general method, for example, by combining P-alkylbenzoic acid and the above alcohol with sulfuric acid,
Using a catalyst such as P-toluenesulfonic acid or phosphoric acid,
This can be easily carried out by dehydration reaction at 65°C to 130°C. P-dialkylbenzoic acid used as a raw material is commercially available, but if necessary, it can also be obtained by reacting amine benzoic acid with methyl bromide, ethyl bromide, propyl bromide, or isopropyl bromide.

2,4, consisting of lophine dimer used in the present invention
5-triarylimidazolyl dimer (as el,
Compounds of the formula Φ consisting of lophine dimers linked together by a single covalent bond, i.e. (optionally substituted with the phenyl group), N
J Eva, 2-(0-chlorophenyl)-4,5-Schifz
Nylimidazolyl dimer 9, 2-(0-fluorophenyl)-4115-diphenylimidazolyl dimer, 2-
(0-chlorophenyl)-4-5-bis-(m-methoxyphenyl)imidazolyl dimer, 1-j, 2-(0
-methoxyphenyl)-4@5-diphenyl imidazolyl dimer, 2-(P-methoxyphenyl)-4.5-
diphenylimidazolyl dimer, 2,4-di(P-methoxyphenyl)5-phenylimidazolyl dimer, 2-
(2', 4-, dimethoxyphenyl)-4, 5-diphenyl memidazolyl dimer, 2-(P-methylmercaptophenyl)-4, 5-diphenylimidazolyl dimer,
Examples include hexaphenyllophine dimer, bis(2,3,5-triphenylimidazolyl) dimer, and the like. Suitable lophine dimers are described in GB 997,396 and GB 1,047,569.

In the present invention, a coloring agent, a color former, such as a leuco dye, may be contained, and it is more preferable to contain a leuco dye, a color former. can act together as a role and free radical generator. Particularly effective leuco dyes are those having at least one dialkyl ζ group. Also, any amine-substituted leucotriphenylmethane dye or various salts of the dye may be used, such as the hydrochloride salt of the leuco blue dye. Specific examples of suitable dyes include, for example, tris-(4-N.N-
diethylamino-〇-)lyl)metatrihydrochloride, bis(
4-N-N-diethyl 7f/-0-)1 thenylmethane, bis(4-N-N-diethyl 2)-〇-tolyl)-benzylthiophenylmethane, leucomalachite green CC, 1, basic, green 4) Crystal violet and brilliant green Royco cedar 1
1 (c, I, basic, green l), Victoria Green 3 B (c, I.

Basic, Green 4), Acid Green GG (c
, 1, Azide Green 3), Methyl Violet (c,
1, basic violet 1), roseanine (c, 1)
, basic violet 14). Salt forms of leuco dyes - for example hydrochlorides, salts with Lewis acids, sulfates,
Although it is possible to use P-toluenesulfonate,
Free bases are preferred -0 Other free radical generating agents that may be used include, for example:
Aniline, N-methylaniline, N・N-diethylaniline, N@N-diethylcresidine, triethanolane, 2-allylthiourea, sarcosine, N-N-diethylglycine, trihexylamine, diethylcyclohexylamine , N・N・N/ , N/-tetramethylethylenediamine, diethylaminoethanol, ethylaminoethanol, N -N -N'-N'-ethylenecyaminotetraacetic acid, N-methylpyrrolidone, N-N-
N'-N'-N'-pentamethyldiethylenetriamine, N-N-diethylxylidene, N-N'-dimethylto-4-piperazine, cudiethylpiperidine in N-β-hydro, N-ethylmorpholine and related amination/synthesis. Examples include amines such as amines.

In the present invention, (a) 100 parts by weight of the resin component, (b) photocrosslinkable α,β-unsaturated ethylenic compound 1
0 to 300 parts by weight, preferably 50 to 20011 parts by weight,
(c) Thioxanthone or its alkyl or halogenated derivative (LX-10 parts by weight, (d) P-dialkylaminobenzoyl represented by formula (1) or its ester a1 to 10 parts by weight, (e) Di A quantity QOI of ~10 parts by weight is preferably used, particularly the ratio of component (c) and component (d) is lo: 1 to 1:4'O, preferably ff3:1#-
Preferably, a ratio of 1:3 is used.

In the present invention, In'c can be used for the first time by adding (c) to (dl components as an essential combination v!, to (ed.) and (b) lE components. e) A alone, some h and 2vi, and a certain h in combination produce a completely unexpected effect.The reason for this is not clear, but it is due to the spectral sensitization in photographic chemistry. It is thought that this phenomenon occurs when radicals generated in the three sensitizers mutually perform a complex reaction, as seen in development.

Moreover, even if other sensitizers are added to the above-mentioned combination system, the effect does not change much.

(Function) The photosensitive composition of the present invention is usually applied in the form of a solution dissolved by fusing to a support film such as a polyethylene terephthalate film and dried to form a photosensitivity and used as an image forming material.

And it can be used for forming photoresist images and relief images in the same manner as the conventional products from Ki Image Forming Materials.

(Example) The present invention will be explained below with reference to Examples.

Example 1 Polymethyl methacrylate 60jF Pentaerythritol triacrylate 15p Tetraethylene glycol diacrylate 15f2.4-
Diethylthioxanthone 3PN-N'-
Isoamyl dimethylbenzoate 3P2-(0
-chlorophenyl)-4.5 dimethoxyphenyl imidazolyl dimer IF ethyl violet α2y paramethoxyphenol α12 The above composition was dissolved in methyl ethyl ketone zooy to prepare a photosensitive solution.

This photosensitive solution was applied onto a polyethylene terephthalate film having a thickness of 25 μm so that the photosensitive layer after drying was 501 Alζ, and dried at 80° C. for 10 minutes to prepare a raw image forming material.

Next, this image forming material was laminated under pressure on the surface of a double-sided copper-clad board for printed wiring boards having 5% g through holes whose surface had been cleaned. In this state, the negative with the wiring circuit pattern was brought into close contact with the support and exposed to 100 millijoules per square senna at a distance of 1 m from a 40QW high-pressure water lamp.

Then, at room temperature, support polyethylene tele7 crate film tall,) with dichloroethane, L5 immediately/c! Spray development was performed at d pressure.

At this time, the image was reproduced down to the 30p thin line.

In addition, the sensitivity is Kodak Sensitivity Step Taglet IL2
It was 7 steps.

In addition, when spray development was performed for 200 seconds using trichloroethane and T511e/asf pressure, wrinkles appeared in the resist at the 5X* through-hole area (□).

Next, I performed pyro-copper plating and solder plating, and when I observed the cross section, I could not see any plating defects in the 2007A image.

Further, no gel was formed when the photosensitive solution was left at 30° C. for 8 days.

The plating conditions are as follows.

Copper picrate z+ Co″+ 309/L pH8
, 8-picric acid P, 0. 2009/l
50'C nitrate N0s-8f/L
3A/dWI Ammonia NHs 2
9/L 3G minute orthophosphoric acid HPO"" 4 α19/l Example 2> Poly(methyl methacrylate-methacrylic acid) 602 (
Methyl meccrylate: methacrylic acid concentration 95:5) Pentaerythritol triacrylate 155j Tetraethylene glycol diacrylate 15p2-
Chlorthioxanthone 32N-N
'-Ethyl dimethylbenzoate 3y2-
(0-90rofe;ru)-4,5-dimethoxyphenylimidazolyl dimer 1j'a icomalachite green 12 ethyl violet α2y paramethoxyphenol αl! A photosensitive solution was prepared using the above composition, and development was carried out according to the procedure of Example 10.

At this time, at the time of exposure, the exposed area developed a bright green color, and a colored snow image was obtained.

At this time, the image was reproduced down to the thin line of sep.

Moreover, the sensitivity was 6 steps with Kodak Sensitivity Step Tablet X2.

Further, spray development was carried out using trichloroethane and L5#/- pressure for 500 seconds, but there was no abnormality in the resist tenting the through-hole portion of the SOX film.

Next, in the same manner as in Example 1, pyro-copper plating and solder plating were performed, and cross-sectional observation was performed. No plating spots 9 were observed in the 200p image.

Further, no gel was formed even when the photosensitive solution was left at 30° C. for 30 days.

Comparative Example 1> Polymethyl methacrylate 60f Pentaerythritol triacrylate 15y Tetraethylene glycol diacrylate 15y Penzotsenone 3P Mihira
− Ketones
1 y Ethyl violet α 2 y Paramethoxyphenol α 12 A photosensitive solution was prepared using the composition described above, and development was carried out according to the procedure of Example 10.

At this time, the image was only reproduced up to the 60H line.

Also, the sensitivity was as low as 4 to 5 steps with Kudatsu Sensitivity Step Tablet 2.

Further, when spray development was carried out with trichloroethane at a pressure of L5KF/- for 200 seconds, wrinkles appeared in the resist at the through-hole portions of 5% m.

(Effects) Since the recombinant photosensitive resin has the above-mentioned structure, it can be used as an image forming material and has a sensitizing effect that quickly forms a photoimage, and the photosensitive liquid is extremely stable during storage. It is stable and easy to use, and the adhesion between the cured photosensitive layer and the substrate surface and the hardening of the film are significantly improved, which leads to a good result in the stabilization phenomenon and the resolution in solvent development. When used as a copper resist, the etching resistance of the photosensitive layer is excellent, and there is little deterioration in high resolution.When used as a one-way copper resist, it has strong tenting properties, and when used as a metal resist, it has excellent etching resistance. It is effective for use in applications that require precision, such as the manufacture of printed wiring boards, as there is no slippage.

Claims (1)

[Scope of Claims] 1. (a) a resin having an α,β-unsaturated ethylenic monomer as a constituent unit, (b) a photocrosslinkable α,β-unsaturated ethylenic compound that is liquid at room temperature, (c ) At least one type of thioxanthone or its alkyl or halogenated derivative; (d) At least one type of P-dialkylaminobenzoic acid represented by formula (I) or its ester; ▲Mathematical formula, chemical formula, table, etc.▼ Formula (I) (However, R_1 and R_2 are alkyl groups having 1 to 3 carbon atoms, R_3 is hydrogen or an alkyl group having 18 or less carbon atoms) (e) 2,4,5-triarylimidazolyl consisting of a lophine dimer A photosensitive resin composition containing at least one type of dimer.